US8044145B2 - Cross-linkable fluoroelastomer, its composition and cross-linked rubber molded product - Google Patents

Cross-linkable fluoroelastomer, its composition and cross-linked rubber molded product Download PDF

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US8044145B2
US8044145B2 US11/740,523 US74052307A US8044145B2 US 8044145 B2 US8044145 B2 US 8044145B2 US 74052307 A US74052307 A US 74052307A US 8044145 B2 US8044145 B2 US 8044145B2
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cross
fluoroelastomer
linkable
absorption peak
linkable fluoroelastomer
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Masahide Yodogawa
Masayuki Saito
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

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  • the present invention relates to a fluoroelastomer capable of exhibiting an excellent cross-linking reactivity and a high cross-linking rate, a fluoroelastomer composition containing it, and a cross-linked rubber molded product excellent in the cross-linked physical properties.
  • a tetrafluoroethylene/propylene copolymer (hereinafter referred to also as a TFE/P copolymer) is used as a rubber material excellent in the heat resistance and chemical resistance in such a severe environment that ordinary rubber materials are not durable.
  • the TFE/P copolymer is poor in the cross-linking reactivity at the time of producing a rubber product.
  • a method for improvement a method of carrying out heat treatment at a high temperature for a long time was proposed (e.g. Patent Document 1). However, by such a method, the production efficiency was inadequate, since it required heat treatment at a high temperature over a long time.
  • a fluoroelastomer composition obtained by incorporating various blend materials to the heat-treated TFE/P copolymer obtained by this method was excellent in a cross-linking reactivity when it was molded and cross-linked by means of a mold, but its mold release characteristics were not necessarily adequate.
  • the present inventors have found that when an organic peroxide is mixed to a fluoroelastomer poor in the cross-linking reactivity, followed by heat treatment, its cross-linking reactivity can be remarkably improved. Further, it has been found that a fluoroelastomer composition obtained by using the obtained fluoroelastomer, is excellent in the mold release characteristics when it is molded and cross-linked by means of a mold. Further, it has been found that when the fluoroelastomer composition obtained by using the obtained fluoroelastomer is cross-linked, a cross-linked rubber molded product excellent in the cross-linked rubber physical properties can be obtained. Thus, the present invention has been accomplished.
  • the present invention provides a cross-linkable fluoroelastomer having a Mooney viscosity of from 20 to 300, obtainable by heat-treating a mixture of a fluoroelastomer (A) and an organic peroxide (B) at a temperature of from 110 to 380° C. for from 10 seconds to 3 hours.
  • the present invention provides the above cross-linkable fluoroelastomer, of which the infrared absorption spectrum has an absorption peak at from 1,640 to 1,700 cm ⁇ 1 .
  • the present invention provides the above cross-linkable fluoroelastomer, wherein the intensity of the absorption peak at from 1,640 to 1,700 cm ⁇ 1 of the infrared absorption spectrum as represented by absorbance is from 0.01 to 5.0.
  • the present invention provides the above cross-linkable fluoroelastomer, of which the infrared absorption spectrum as represented by absorbance has no absorption peak at from 1,740 to 1,800 cm ⁇ 1 or has an absorption peak at from 1,740 to 1,800 cm ⁇ 1 with an absorption peak intensity of at most 2.0.
  • the present invention provides the above cross-linkable fluoroelastomer, wherein the blend ratio of the organic peroxide (B) is from 0.1 to 10 parts by mass per 100 parts by mass of the fluoroelastomer (A).
  • the present invention provides the above cross-linkable fluoroelastomer, wherein the fluoroelastomer (A) is a tetrafluoroethylene/propylene copolymer.
  • the present invention provides the above cross-linkable fluoroelastomer, wherein the temperature for half life of one minute of the organic peroxide (B) is from 110 to 300° C.
  • the present invention provides a method for producing a cross-linkable fluoroelastomer, which comprises heat-treating a fluoroelastomer (A) and an organic peroxide (B) at a temperature of from 110 to 380° C. for from 10 seconds to 3 hours.
  • the present invention provides the above method, wherein the fluoroelastomer (A) and the organic peroxide (B) are kneaded by means of an extruder.
  • the present invention provides a fluoroelastomer composition
  • a fluoroelastomer composition comprising the above cross-linkable fluoroelastomer, a cross-linking agent (C) and a cross-linking assistant (D).
  • the present invention provides a cross-linked rubber molded product obtained by cross-linking the above fluoroelastomer composition.
  • the present invention provides a cross-linked rubber molded product obtained by cross-linking the above cross-linkable fluoroelastomer by applying an ionizing radiation thereto.
  • the cross-linkable fluoroelastomer of the present invention is excellent in rubber elasticity and cross-linking reactivity, and the cross-linked rubber molded product is excellent in cross-linked rubber physical properties and excellent in heat resistance, chemical resistance, weather resistance, mold release characteristics, etc.
  • cross-linkable fluoroelastomer of the present invention is far superior in the productivity as compared with the prior art, and the cross-linkable fluoroelastomer composition is excellent also in mold release characteristics.
  • FIG. 1 is a chart showing infrared absorption spectra of one embodiment of the cross-linked fluoroelastomer of the present invention and fluoroelastomers of the prior art.
  • FIG. 2 is a view showing the method for obtaining the intensity of each absorption peak top in the infrared absorption spectra in FIG. 1 .
  • fluoroelastomer (A) to be used in the present invention a known fluoroelastomer may be employed. Particularly, a fluoroelastomer having no cross-linkable functional groups may suitably be employed.
  • the cross-linkable functional group may, for example, be a carbon-carbon unsaturated bond, iodine, bromine, a cyano group or a hydrolysable silyl group.
  • the fluoroelastomer (A) include a tetrafluoroethylene/propylene copolymer, a tetrafluoroethylene/propylene/vinylidene fluoride copolymer, a vinylidene fluoride/hexafluoropropylene copolymer, and a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer.
  • a tetrafluoroethylene/propylene copolymer poor in the cross-linking reactivity is preferred.
  • the tetrafluoroethylene/propylene copolymer may be one obtained by copolymerization of tetrafluoroethylene (hereinafter referred to as TFE) and propylene (hereinafter referred to as P) only, or may be one obtained by copolymerization of TFE and P with other monomers.
  • TFE tetrafluoroethylene
  • P propylene
  • Such other monomers may, for example, be hexafluoropropylene, vinylidene fluoride, a perfluorovinyl ether of the formula CF 2 ⁇ CF—O—R f (wherein R f is a C 1-8 saturated perfluoroalkyl group or a perfluoro(alkoxyalkyl) group), an ⁇ -olefin such as ethylene or butene (excluding propylene) and a vinyl ether such as methyl vinyl ether or ethyl vinyl ether.
  • Such other monomers may be used alone or in combination as a mixture of two or more of them.
  • the content of repeating units based on other monomers is preferably from 0 to 30 mol %, more preferably from 0 to 15 mol %.
  • any conventional method may be used.
  • emulsion polymerization solution polymerization, suspension polymerization or bulk polymerization may, for example, be mentioned.
  • a radical polymerization initiator, a redox polymerization initiator, heat, radiation, etc. may be employed.
  • Emulsion polymerization is preferred, whereby adjustment of the molecular weight and the copolymer composition is easy, and it is excellent in productivity.
  • the cross-linkable fluoroelastomer of the present invention is obtainable by heat-treating a mixture of the above fluoroelastomer (A) and an organic peroxide (B). By the heat treatment, its cross-linking reactivity will be remarkably improved.
  • Such an organic peroxide (B) is preferably an organic peroxide having a temperature of half life of one minute (a temperature at which its half life is one minute) being from 110 to 300° C., more preferably from 110 to 250° C., most preferably from 110 to 200° C.
  • dicumyl peroxide 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane and dibenzoyl peroxide.
  • dicumyl peroxide 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane or di-tert-butyl peroxide. More preferred is dicumyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, tert-butylperoxybenzoate or 2,5-dimethyl-2,5-dibenzoyl peroxyhexane.
  • organic peroxides (B) may be used alone or in combination as a mixture of two or more of them.
  • the blend amount of the organic peroxide (B) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 7 parts by mass, per 100 parts by mass of the fluoroelastomer (A). Within such a range, cross-linkable functional groups will be introduced into the fluoroelastomer (A), and a cross-linkable fluoroelastomer excellent in cross-linkability can be obtained.
  • the heat-treating temperature is preferably from 110 to 380° C. Such a temperature range agrees to the temperature for half life of one minute of the organic peroxide to be incorporated, whereby the reaction for introduction of cross-linkable functional groups by the organic peroxide will be facilitated. More preferably, it is from 150 to 320° C., most preferably from 150 to 300° C. Within such a range, there will be little heat decomposition of the polymer and a cross-linkable fluoroelastomer excellent in cross-linking reactivity can be obtained.
  • the heat-treating time is preferably from 10 seconds to 3 hours. By such a heat-treating time, a cross-linkable fluoroelastomer excellent in cross-linking reactivity can be obtained.
  • the Mooney viscosity of the cross-linkable fluoroelastomer of the present invention is from 20 to 300, preferably from 20 to 270, more preferably from 30 240, most preferably from 30 to 200.
  • the Mooney viscosity is an index for the molecular weight. Namely, the larger the Mooney viscosity, the higher the molecular weight, and the smaller the Mooney viscosity, the lower the molecular weight. Within such a range, the processability of the fluoroelastomer, and the cross-linked rubber physical properties will be good.
  • Such a Mooney viscosity is a value to be measured in accordance with JIS K6300 using a large rotor having a diameter of 38.1 mm and a thickness of 5.54 mm at 100° C. by setting the preheating time to be one minute and a rotor rotational time to be 4 minutes.
  • the cross-linkable fluoroelastomer of the present invention has an absorption peak at from 1,640 to 1,700 cm ⁇ 1 in its infrared absorption spectrum. More preferably, it has an absorption peak at from 1,660 to 1,700 cm ⁇ 1 in the infrared absorption spectrum. More preferably, it has an absorption spectrum at from 1,680 to 1,700 cm ⁇ 1 .
  • the absorption peak within such a range is attributable to a carbon-carbon unsaturated bond.
  • Such an absorption peak is not observed with a fluoroelastomer (A) before the heat treatment, and accordingly, it is considered that during the heat treatment of the mixture with the organic peroxide, an unsaturated bond has been introduced by such a mechanism that a hydrogen atom of the fluoroelastomer (A) is withdrawn.
  • the cross-linkable fluoroelastomer having an absorption peak within this range is excellent in the cross-linkability.
  • the peak intensity of the infrared absorption spectrum as represented by absorbance is preferably from 0.01 to 5.0, more preferably from 0.02 to 2.0, further preferably from 0.03 to 1.8, most preferably from 0.05 to 1.5.
  • the cross-linkable fluoroelastomer having the absorption peak intensity within this range is excellent in the cross-linkability.
  • the cross-linkable fluoroelastomer of the present invention preferably has no absorption peak or a small absorption peak at from 1,740 to 1,800 cm ⁇ 1 in its infrared absorption spectrum.
  • the peak intensity of the absorption peak at from 1,740 to 1,800 cm ⁇ 1 in the infrared absorption spectrum represented by absorbance is preferably at most 2.0, more preferably at most 0.2, further preferably at most 0.02, still further preferably at most 0.002, most preferably no peak being observed.
  • An absorption peak within this range is considered to be attributable to a functional group such as a hydroxycarbonyl group formed by modification of e.g. a polymer terminal. If the cross-linkable fluoroelastomer has an absorption peak having high intensity within this range, such an elastomer tends to be poor in the mold release properties.
  • the heat treatment is carried out preferably by using a heating oven, an extruder, a kneader or the like.
  • a method for producing a cross-linkable fluoroelastomer of the present invention preferred is a method for producing a cross-linkable fluoroelastomer wherein the fluoroelastomer (A) and the organic peroxide (B) are kneaded by means of an extruder at a temperature of 110 to 380° C. for from 10 seconds to 3 hours.
  • the kneading time when an extruder is employed is more preferably from 10 seconds to 30 minutes, most preferably from 10 seconds to 15 minutes.
  • a method for producing a cross-linkable fluoroelastomer may be mentioned wherein a mixture of particles of the fluoroelastomer (A) and particles or liquid of the organic peroxide (B), is molded and heat-treated at a temperature of from 110 to 380° C. for from 10 seconds to 3 hours. It is preferred to use a two-roll mill or a kneader for the mixing or kneading of the particles of the fluoroelastomer (A) and the particles or liquid of the organic peroxide (B).
  • the fluoroelastomer composition comprising the cross-linkable fluoroelastomer of the present invention, a cross-linking agent (C) and a cross-linking assistant (D) is excellent in cross-linkability and also excellent in mold-release properties.
  • cross-linking agent (C) an organic peroxide is preferred, and those known as cross-linking agents for rubber may all be used.
  • dicumyl peroxide 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane or di-tert-butyl peroxide. More preferred may, for example, be dicumyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, tert-butylperoxybenzoate or 2,5-dimethyl-2,5-dibenzoyl peroxyhexane.
  • Cross-linking agents of component (C) may be used alone or in combination as a mixture of two or more of them.
  • the content of the cross-linking agent is preferably from 0.3 to 10 parts by mass, more preferably from 0.3 to 5 parts by mass, most preferably from 0.5 to 3 parts by mass, per 100 parts by mass of the cross-linkable fluoroelastomer. Within such a range, it is possible to obtain a cross-linked rubber excellent in the balance of tensile strength and elongation.
  • an unsaturated polyfunctional compound is preferred.
  • an unsaturated polyfunctional compound By an unsaturated polyfunctional compound, the cross-linking efficiency can be made high.
  • conventional ones may all be used. Specific examples include triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate oligomer, trimethallyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, m-phenylenediamine bismaleimide, p-quinonedioxime, p,p′-dibenzoyl quinonedioxime, di-propargyl terephthalate, diallyl phthalate, N,N′,N′′,N′′′-tetraallyl terephthalamide, and a vinyl group-containing siloxane oligomer such as polymethylvinyl siloxane or polymethylphenylvinyl si
  • triallyl cyanurate, triallyl isocyanurate or trimethallyl isocyanurate is particularly preferred, and triallyl isocyanurate is more preferred.
  • cross-linking assistants of component (D) may be used alone or in combination as a mixture of two or more of them.
  • the content of the cross-linking assistant of component (D) is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 7 parts by mass, per 100 parts by mass of the fluoroelastomer. Within such a range, it is possible to obtain cross-linked rubber physical properties having a good balance of the strength and elongation.
  • a reinforcing material, a filler, an additive, etc. may suitably be incorporated.
  • a reinforcing material and filler a reinforcing material and filler for rubber which have been commonly used for the production of cross-linked rubber may, for example, be mentioned.
  • carbon black such as channel black, furnace black, acetylene black or thermal black
  • an inorganic reinforcing material such as white carbon, magnesium carbonate, surface-treated calcium carbonate
  • an inorganic filler such as calcium carbonate, clay, talc, silica, diatomaceous earth, alumina or barium sulfate, or other fillers
  • an additive such as a pigment, an antioxidant, a stabilizer, a processing aid or an internal mold release agent, may, for example, be mentioned.
  • Such reinforcing materials, fillers and additives may, respectively, be used alone or in combination as a mixture of two or more of them.
  • the blend amount of the reinforcing material may suitably be selected, but it is preferably from 1 to 100 parts by mass per 100 parts by mass of the fluoroelastomer.
  • the blend amount of the filler may suitably be selected, but it is preferably from 1 to 100 parts by mass per 100 parts by mass of the fluoroelastomer.
  • At least one of rubbers such as other fluororubbers, EPDM, silicone rubber and acyl rubber, and resins such as fluororesins, may be incorporated.
  • a fluoroelastomer composition of the present invention it is desirable to uniformly mix the cross-linkable fluoroelastomer, the unsaturated polyfunctional compound, the organic peroxide, and, if necessary, an oxide and/or hydroxide of a bivalent metal, a fluororubber, other reinforcing material, filler, processing aid, additive, etc.
  • Such mixing can be carried out by means of a roll mill for kneading rubber, a kneader or a Banbury mixer which has been commonly used.
  • the working conditions for the mixing are not particularly limited, but usually, the added blend components can adequately be dispersed and mixed in the fluoroelastomer by kneading at a temperature of from about 30 to 80° C. for from about 10 to 60 minutes. Further, such added blend components may be dissolved and dispersed in a suitable solvent to form a suspension solution. Otherwise, the mixing may be carried out by so-called wet mixing, which is carried out in a solvent from the beginning. In such a case, a blend composition in a solution state may be obtained by using a mixing machine such as a roll mill, a ball mill or a homogenizer.
  • the optimal conditions should better be selected depending upon the purpose or types of the starting materials to be used and the blend product.
  • the fluoroelastomer composition of the present invention may be formed into molded products such as seals, packings, sheets, pipes, rods, tubes, angles, channels, coated fabrics, coated plates or wire coatings by usual molding or other molding methods such as extrusion, transfer, calendering, roll coating, brush coating or impregnation. Otherwise, it may be formed also into profiles or special molding products such as sponge rubbers by various molding methods.
  • composition of the present invention is cured by heating.
  • a conventional operation may be employed as the operation for such curing.
  • an operation of heating under pressure in a mold may, for example, be employed, or an operation of heating in a heating furnace or a steam oven after the composition is formed by extrusion or calender rolling may be employed.
  • the optimal conditions may be selected for use depending upon the materials to be used or the blend.
  • the temperature for cross-linking by heating is usually at a level of from 60 to 250° C., preferably from 120 to 200° C.
  • the heating time is not particularly limited, but it is usually within a range of from one minute to three hours, preferably within a range of from 5 minutes to two hours, depending upon the type of the organic peroxide. If the heating temperature is increased, the heating time may be shortened.
  • re-heating treatment of the obtainable cross-linked product may also be employed, and such may be useful for improvement of the physical properties. For example, re-heating treatment at a temperature of from 150 to 250° C., preferably from 180 to 230° C., for from about 2 to 25 hours, may be employed.
  • the cross-linkable fluoroelastomer of the present invention may be cross-linked by irradiation with an ionizing radiation without incorporating component (C) or component (D). Otherwise, after mixing components (C) and (D), it may be cross-linked by irradiation with the radiation.
  • the ionizing radiation electron rays or ⁇ -rays may, for example, be mentioned.
  • a suspension solution having the fluoroelastomer composition of the present invention dissolved and dispersed in a suitable solvent is applied by e.g.
  • the exposure dose by irradiation with electron rays may suitably be selected, but it is usually preferably from 1 to 300 kGy, more preferably from 10 to 200 kGy.
  • Measurements of the composition and the intensity of an absorption peak in infrared (IR) were carried out as follows.
  • One gram of the fluoroelastomer was sampled and pressed to a thickness of about 0.2 mm by hot pressing at 170° C., and using this pressed product, measurement of the transmission infrared absorbance was carried out by FT-IR (PROTEGE 460, manufactured, by Nicolet).
  • the intensity of the absorption peak top present at from 1,640 to 1,700 cm ⁇ 1 is obtained, as represented by absorbance, from the height perpendicular from a line connecting the intensities at two points of 1,630 cm ⁇ 1 and 1,710 cm ⁇ 1 , and represented by the absorbance calculated as corresponding to a thickness of 0.2 mm.
  • the strength of the absorption peak top is obtained from the height perpendicular from a line connecting the intensities at two points of 1,730 cm ⁇ 1 and 1,810 cm ⁇ 1 , and represented by an absorbance calculated as corresponding to a thickness of 0.2 mm.
  • the fluoroelastomer composition was subjected to press cross-linking at 170° C. for 10 minutes without using a release agent, and immediately after the completion, a sample with a width of 50 mm was pinched by a clip, and the force for releasing it perpendicularly from the die in a longitudinal direction of 130 mm, was measured by a pull gauge. The measurement was repeated 25 times, and the average value was taken.
  • the unit was g/50 mm.
  • a fluoroelastomer composition was subjected to measurement of the cross-linking properties by means of a cross-linking property measuring apparatus (RPA, manufactured by Alpha Technologies) at 177° C. for 12 minutes under a condition of an amplitude of 3 degrees.
  • MH represents the maximum value of the torque
  • ML represents the minimum value of the torque
  • MH-ML represents the cross-linking density (also called the vulcanization density).
  • the infrared absorption spectrum of the obtained cross-linkable fluoroelastomer is shown in FIG. 1 .
  • Example 2 Treatment was carried out under the conditions as shown in Table 1 in the same manner as in Example 1 except that only the organic peroxide used was changed, whereby a cross-linkable fluoroelastomer was obtained.
  • Example 2 tert-butylcumyl peroxide (Perbutyl C, manufactured by NOF CORPORATION, temperature for half life of one minute: 173.3° C.) was used.
  • Example 3 1,3-bis(tert-butyl peroxyisopropyl)benzene (Perbutyl P, manufactured by NOF CORPORATION, temperature for half life of one minute: 175.4° C.) was used.
  • Example 5 Treatment was carried out under the conditions as shown in Table 1 in the same manner as in Example 1 except that the organic peroxide used and the heat-treating conditions were changed, whereby a cross-linkable fluoroelastomer was obtained.
  • di-tert-butyl peroxide Perbutyl D, manufactured by NOF CORPORATION, temperature for half life of 1 minute: 185.9° C.
  • the TFE/P copolymer as used in Example 1 was put into a single screw extruder set at 300° C. and extruded for a retention time of two minutes.
  • the infrared absorption spectrum of the obtained TFE/P copolymer is shown in FIG. 1 .
  • the TFE/P copolymer as used in Example 1 was subjected to heat treatment for 15 hours by using an oven of 300° C.
  • the infrared absorption spectrum of the obtained TFE/P copolymer is shown in FIG. 1 .
  • Example 1 The infrared absorption spectrum of the TFE/P copolymer used in Example 1 is shown in FIG. 1 .

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US20100196709A1 (en) * 2007-11-20 2010-08-05 Asahi Glass Company, Limited Cross-linkable fluoroelastomer excellent in cross-linkability and method for its production
WO2016024938A1 (en) * 2014-08-09 2016-02-18 Agc Chemicals Americas, Inc. Fluoropolymer compositions and uses thereof
US10584186B2 (en) 2015-07-22 2020-03-10 Bridgestone Corporation Silane-functionalized polymer and process for making and using same

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JP5527204B2 (ja) 2008-05-20 2014-06-18 旭硝子株式会社 含フッ素弾性共重合体組成物およびその架橋ゴム部材
GB2462079A (en) * 2008-07-21 2010-01-27 Walker & Co James Ltd Fabric coated with peroxide containing fluoroelastomer composition
JP5663218B2 (ja) * 2010-07-09 2015-02-04 オリンパス株式会社 熱可塑性樹脂組成物及びその製造方法
CN105579521B (zh) * 2013-09-25 2017-04-26 旭硝子株式会社 含氟弹性体组合物、其制造方法、成型体、交联物、以及包覆电线
EP3728493A1 (de) * 2017-12-18 2020-10-28 3M Innovative Properties Company Durch aktinische strahlung fluorierte elastomere und verfahren dafür
CN108841017B (zh) * 2018-05-21 2021-09-14 山西福诺欧新材料科技股份有限公司 一种提高四丙氟橡胶交联活性的热处理方法
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EP1860123B1 (de) 2012-01-18
ATE541867T1 (de) 2012-02-15
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